Dyeing vinyl polymers



Patented Nov. 7, 1944 DYEING VINYL POLYMERS Karl lleymann, Meadvilie, Pa., assignor to American V iscose Corporation, Wilmington, Del, a

corporation of Delaware No'Drawing. Application March 7, 1940,

' Serial No. 322,843

16 Claims. (01. 8-55) This invention relates to improvements in methods of dyeing yarns and other shapes comprising materials that are not readily permeable to water. More particularly, the invention relates to improvements in methods of dyeing yarns and other shapes comprising vinyl polymers, such as polymers of vinylchloride and copolymers of vinyl acetate and vinyl chloride.

This application is a continuation in part-of my application Serial Number 311,109, filed December 27, 1939.

Materials that are not readily permeable to water can not be satisfactorily dyed by the ordinary dyeing procedure used in dyeing cotton, wool, natural silk and regenerated cellulose. when ordinary methods of dyeing are attempted the dye either does not penetrate the material and no dyeing is eflected or when dyeing is effected the color is not fast and leaches out.

Yarns and other shapes of cellulose acetate which are not readily permeable to water have been dyed when treated with a liquid swelling agent, such as alcohol, acetone or acetic acid. The swelling agent forms or opens pores in the material into which the dye penetrates. There are certain objections to the use of liquid swelling agents. Generally a large amount of swelling agent is required. Also the swelling agent has a tendency to weaken the yarn or shape.

I have discovered that yarns and other shapes comprising vinyl polymers, such as polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride can be successfully dyed with suspension dyestuil's when the dyeing operation is carried out in the presence of suspensions of certain normally solid organic compounds which have a solubility in polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride of 2% or greater under the conditions at which the dyeing is carried out. By the term suspension dyestufls is meant dyestufis of the type applicable to cellulose acetate from a dispersion (insoluble anthraquinone and azo dyes) sometimes-referred to as disperso1 dyes, and the dyestuffs referred to hereinafter in the examples by their trade names, are of this type. The compounds which are related to as assistants include:

Thio-p-naphthol p-Chlorothymoi zs-dichloro s-nanhthol zgbdichloroaniline 2,5-dichloroaniline p-Chlorobenzaldehyde a-Naphthylamine- 2,4-dimethoxybenzalde- 'p-Naphthylamine hyde Phenyl-a-naphthylp-Dlmethylaminobenzamine aldehyde Phenyl-s-naphthylo-Hydroxyacetophenone amine Benzophenone o-Aminodiphenyl v p-Hydroxybenzophe- Desoxybenzoin none Fluorenone Methyl-s-naphthylke- B-hydroxyquinoline tone Dibenzyl succinate Camphor Methyl-p-bromobenzo- Benzalacetone ate Anisalacetone Diphenyl phthalate Benzoylacetone p-Naphthyl acetate Benzalacetophenone Phenyl glycine ethylesterl-hydroxy-2-acetonaph- Diphenyl carbonate thone Di-o-cresyl carbonate p-Methoxybenzophe- 2,4,6 tribromophenyl none acetate Benzil a-Naphthyl acetate Diphenyltriketone o-Diphenyl acetate Dibenzoylmethane Ethylene dibenzoate Benzhydrol ycerol tribenzoate Phenylbenzylcarbinol Dlcyclohexyl Phthalate Fluorenyl alcohol Dibenzyl phthalate 's,p'-Diphenoxydiethyl- Phenyl benzoate ether m-Cresyl benzoate p-Methoxydiphenyl p-Cresyl benzoate Benzyl-a-naphthylether p-Aminodiphenyl p-Naphthylmethylether N,N-diphenyl ethyl car- Methoxybenzophebamate none p-Naphthonitrile Benzoic anhydride in carrying out my improved method of dyeing a suspension of a single assistant or several assistants together may be used. The assistant is,-

for example, dissolved in a suitable solvent, such as alcohol, and the assistant in solution and a suitable dispersing agent, such as that known in the trade as Igepon T, are added to the dye bath. The .dye bath contains a suspension dyestuff. The assistant is precipitated in the dye bath in colloidal or very finely divided form. When amino compounds are used as assistants they may be dissolved in an acid solution and precipi tated and dispersed in an alkaline dye bath. Phenols may be dissolved in an alkaline solution and precipitated and dispersed in an acid dye bath. Satisfactory results are also obtained under certain conditions when the phenol solution is added to the dye bath and is not dispersed. The yarn or shape to be dyed is treated with the dye bath containing the assistant in the ordinary manner. This procedure may be followed using 7 various quantities of dyestufl and assistants with diiferent dye bath ratios and temperatures of the dye baths depending upon the character of the material being dyed and the type of dyeing that is being carried out. A satisfactory procedure is one in which the dye bath ratio is 1:30 and contains 1.5% suspension dyestufi with or less of assistant based on the weight of the yarn or shape to be dyed. A suitable dye bath temperature is about 50 C. and the duration of the dyeing operation one hour. Other temperatures may also be used.

My invention may also be carried out by applying the assistant from suspension directly to the yarn or shape. When the yarn or shape is thereafter immersed in the dye bath the assistant aids the action oi the dye. bath on the yarn or shape in the same mane: as'when it has been added to the dye bath. 7

Instead of using either of the above methods, I may add the assistant directly to the vinyl polymers before the yarn or shape is formed. The yarn or shape containing the assistant is treated with the dye bath in the ordinary manner.

The following examples are illustrative of the invention:

Example 1.Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dy baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestud and 5% l3- naphthol based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Cibacete Orange 2R Cibacete Scarlet G Acele Violet B Acele Yellow 3G bath was also used with Cibacete Scarlet G 1% and Acele Violet B 1% as the dyestufi.

Example 2.-Yarns comprising copolyrners of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestufi and 5% P 'methylamino-benzaldehyde based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Celliton Red Violet RR Phenacyl Navy Blue PV Phenacyl Red R Celutate Brill. Blue B Cibacete Rubine BS Artisil Direct Yellow 3GP Example 3.-Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of l:30.and containing 1.5% suspension dyestufi and 1.5% homephenone based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Celliton Fast Pink BA Acele Scarlet G Calonese Orange 3R0 Cibacete Violet B- Celutate Fast Blue GL Artisil Direct Yellow 3G ex. Phenacyl Red R Example 4.Yarns comprising oopolymers of vinyl acetate and vinyl chloride were dyed in ascasvo I baths having a dye bath ratio of 1:30 and con taining 1.5% suspension dycstufl and 5% o-hy= droxydiphenyl based on the weight of the y. The temperatures of the dye baths were 60 C.

and the duration of the dyeing operation one hour. The dyestufis that were used were Example 5.Yarns comprising oopolymers of vinyl acetate and vinyl chloride were treated with a bath in a ratio of 1:30 containing 5% 0-115!- droxydiphenvl based on the weight of the yarn at a temperature of 60 C. and for a period of one-half hour. The yarns so treated were then dyed by immersing in dye baths having a, dye bath ratio of 1:30 and containing 1.5% suspension dyestufi based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestufls that were used were Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 36? ex. cone. Celliton Fast Brown 53A w While preferred assistants and procedures have been shown it is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined ln the appended claims.

What I claim is:

1. A method of dyeing yarns and other shapes comprising vinylpolymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuif, in the presence of a water-insoluble, normally solid organic compound selected from the group consisting of dibenzyl succinate, methyl-p-bromobenzoate, diphenyl phthalate, fl-naphthyl acetate, phenyl glycine ethyl-ester, diphenyl carbonate, di-o-cresyl carbonate, 2,4,6 tri-bromophenyl acetate, a-naphthyl acetate, o-diphenyl acetate, ethylene dibenzoate, glycerol tribenzoate, dicyclohexyl phthalate, dibenzyl phthalate... phenyl benzoate, m-cr'esyl benzoate and p-cresyl benzoate.

2. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuff, in the presence of a waterinsoluble, normally solid organic compound selected from the group consisting of dibenzyl succinate, methyl-p-bromobenzoate, diphenyl phthalate, p-naphthyl acetate, phenyl glycine ethyl-ester, diphenyl carbonate, di-o-cresyl carbonate, 2,4,6 tribromophenyl acetate, -naphthyl acetate, o-diphenyl acetate, ethylene dlbenzoate,

glycerol tribenzoate, dioyclohexyl phthalate, di-

dye benzoate and p-cresylbenzoate.

l ll!!! 7 2,309,370 3. A method ofdyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufl and a water-insoluble, normally solid organic compound selected from the group consisting of dibenzyi succinate, methyl-p-bromobenzoate, diphenyl phthalate, B-naphthyl acetate, phe'nyl glycine ethylester, diphenyl carbonate, di-o-cresyl carbonate, 2,4,6 tribromophenyl acetate, a-naphthyl acetate, o diphenyl acetate, ethylene di-benzoate,

glycerol trlbenzoate, dicyclohexyl phthalate, di-

benzyl phthalate, phenyl benzoate, m-cresyl benzoate and p-cresyl benzoate suspended in the dye bath.

4. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step or treating the yarn or shape with an aqueous dye bath containing a suspension dyestufl, and a water-insoluble, normally solid organic compound selected from the roup consisting o'i! dibenzyl succinate, methyl-pbromobenzoate, diphenyl phthalate, fi-naphthyl acetate, phenyl glycine ethylester, diphenyl carbonate, di-o-cresyl carbonate, 2,4,6 tribromophenyl acetate, u-naphthyl acetate, o-diphenyl acetate, ethylene dibenzoataglycerol tribenzoate,

-dicyclohexyl phtha1ate,dibenzyl phthalate, phenyl benzoate, m-cresyl benzoate and. p-cresyl benzoate suspended in the dye bath.

5. A method oi dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufl in the presence'of dibenzyl succinate.

6. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestun' in the a presence of methyl-p-hromobenzoate.

'l. A method oi. dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuii' in the presence of diphenyl phthalate.

3 suspension dyestufl in the presence or dibenzyl succinate.

8. A method oi. dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride. comprising the step oi treating the yarn with an aqueous dye bath containing a 9. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treatingthe yarn or shape with an aqueous dye bath containing a suspension dyestufl in the presence or methyl-pbromobenzoate.

10. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step or treating the yarn or shape with an aqueous dye bath containing a suspension dyestufl' in the presence of dlphenyl Phthalate.

.11. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn orshape with an aqueous dye bath containing a suspension dyestuil and dibenzyl'succinate suspended in the dye bath.

12. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the'step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestufl' and bath.

13. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with an aqueous dye hath contain! diphenyl phthalate suspended in the dye bath.

14. A method of dyeing yarns and other shapes comprising copolymers oi vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with anaqueous dye bath containing a suspension dyestufl and dibenzyl succinate suspended in the dye bath.

15. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step 01' treatingthe yarn or shape with an aqueous dye bath containing a suspension dyestuil' and suspended in the dye bath.

16. A method or dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with an aqueous dye bath containing a suspension dyestuir and diphenyl phthalate suspended in the dye bath.

KARL HEYMANN.

ng a suspension dyestuf! and methyl-p-bromobenzoate 

